Composite materials, composite film manufactured by using the same and method for manufacturing composite film

ABSTRACT

The present invention provides a composite material comprising a glass cloth; and an organic-inorganic hybrid composition comprising diphenylsilanediol and alkoxy silane, a composite film manufactured by using the same, and a method for manufacturing the composite film.

This application is a Divisional of U.S. patent application Ser. No.12/738,554, filed on Nov. 16, 2010, which is the national stageapplication of PCT/KR2008/006173, filed on Oct. 17, 2008, which claimsthe benefit of Korean Patent Application Nos. 10-2007-0105173, filed onOct. 18, 2007 and 10-2007-0105176, filed on Oct. 18, 2007, all of whichare hereby incorporated by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a composite material comprising a glasscloth and an organic-inorganic hybrid composition, a composite filmmanufactured by using the same, and a method for manufacturing thecomposite film.

BACKGROUND ART

Although glass plates used for display devices, picture frames,craftwork, containers, or the like are advantageous in that they have asmall coefficient of thermal expansion, superior gas barrier properties,high transparency, good surface flatness, excellent heat resistance andchemical resistance, they tend to break easily and be heavy because oftheir high density.

Recently, as liquid crystal displays, organic light emitting devices,and electronic paper are arousing a growing interest, research onreplacing the glass substrates used in such devices with plasticcounterparts is gaining momentum.

A basic substrate, plastic film and a plastic substrate having afunctional coating layer are advantageous over the glass plate in termsof light weight, ease of design, and impact-resistance. Also, aneconomic advantage may be attained from continuous manufacturing,compared to the glass substrate.

For a plastic substrate to be used in a display device, it should have aglass transition temperature high enough to endure the transistorprocessing temperature and the transparent electrode depositiontemperature, oxygen and water vapor barrier properties so as to preventaging of liquid crystals and organic light emitting materials, a smallcoefficient of thermal expansion and good dimensional stability so as toprevent deformation of the plate due to change of the processingtemperature, mechanical strength comparable to that of the conventionalglass plate, chemical resistance sufficient for enduring the etchingprocess, high transparency, low birefringence, good surface scratchresistance, etc.

Among such properties, a low coefficient of thermal expansion (CTE) is aparticularly important property, and a method of manufacturing a plasticfilm using a glass cloth is one of methods that provide a substratehaving a low coefficient of thermal expansion.

To embody a low coefficient of thermal expansion (CTE), a tightly wovenglass cloth should be used. As a glass cloth has a higher weavingdensity, the prepared plastic film has a lower coefficient of thermalexpansion (see FIG. 4).

However, in the case where a film is manufactured by using the glasscloth along with organic materials such as epoxy and polymer, there is alimit in using a tightly woven glass cloth due to air bubble generatedbetween glass fibers, and cracks may be generated at the interface dueto a low interface adhesion strength between the glass cloth and organicmaterials.

A method of manufacturing films using organic materials and glass clothis exemplified by US 2005/0203239, which discloses a method of dippingand curing a glass cloth in organic materials such as epoxy andpolymers.

In this method, the surface of glass cloth is modified to improve theadhesion strength at the interface between the glass cloth and organicmaterials. However, there is a problem in that cracks are stillgenerated at the interface due to the low interface adhesion strength.

In addition, when a film is manufactured by dipping the glass cloth inorganic materials such as epoxy and polymers, a longer processing timefor curing or solvent evaporation is required, so as to reduce itsproductivity.

Further, when a film is manufactured by dipping the glass cloth inorganic materials such as the known epoxy and polymers, it is difficultto remove air bubble generated between the glass cloths due to highviscosity. In addition, to improve the problem, the process may beperformed at a high temperature or under vacuum conditions, but theprocess becomes complex. Thus, the process cannot be easily performed.

Furthermore, when a film is manufactured by dipping the glass cloth inorganic materials such as the known epoxy and polymers, a laminationprocess is employed. However, there is a problem in that it is difficultto perform a continuous process by the process.

Moreover, since the glass cloth has a wavelength-dependent refractiveindex that is different from that of the organic materials such as theknown epoxy and polymers, it is difficult to manufacture a transparentfilm.

DISCLOSURE Technical Problem

It is an object of the present invention to provide a compositematerial, in which an interface crack and air bubble of glass fiber areprevented and its productivity is improved, a composite filmmanufactured by using the same, and a method for manufacturing thecomposite film.

In addition, it is another object of the present invention to provide atransparent composite material, a transparent composite filmmanufactured by using the same, and a method for manufacturing thetransparent composite film by controlling a refractive index of theorganic-inorganic hybrid composition.

Technical Solution

The present invention provides a composite material comprising a glasscloth; and an organic-inorganic hybrid composition that comprisesdiphenylsilanediol and alkoxy silane.

The present invention provides a composite film comprising a glasscloth; and an organic-inorganic hybrid composition that comprisesdiphenylsilanediol and alkoxy silane, manufactured by using thecomposite material according to the present invention.

The present invention provides an electronic device comprising thecomposite film according to the present invention.

The present invention provides a method for manufacturing the compositefilm, comprising the steps of a) preparing a glass cloth; b) preparingan organic-inorganic hybrid composition in a sol state, comprisingdiphenylsilanediol and alkoxy silane; and c) dipping and curing theglass cloth in the organic-inorganic hybrid composition in a sol state.

According to the present invention, it provides a transparent compositematerial, a transparent composite film, an electronic device comprisingthe transparent composite film, and a method for manufacturing thetransparent composite film cloth by adjusting the refractive index ofthe organic-inorganic hybrid composition for the difference in therefractive indices between the organic-inorganic hybrid compositionafter curing and the glass cloth to be 0.01 or less.

Advantageous Effects

According to the present invention, a composite film is manufactured bysol-gel reaction between an organic-inorganic hybrid composition havinga low viscosity and a short curing time and a glass cloth, and thus theinterface adhesion strength between the glass fiber and theorganic-inorganic hybrid material is improved to prevent generation ofinterface cracks and air bubble at the interface of the glass fiber andthe organic-inorganic hybrid material.

The organic-inorganic hybrid has a short curing time to improveproductivity of the film, whereas a longer processing time for curing orsolvent evaporation is required in the case of using the known epoxy andpolymers.

Productivity can be improved because it is possible to operatecontinuous process wherein film may be produced by repeating the methodcomprising dipping the glass cloth in the organic-inorganic hybridcomposition with low viscosity and short curing time.

According to the present invention, it provides a transparent compositematerial, a transparent composite film, an electronic device comprisingthe transparent composite film, and a method for manufacturing thetransparent composite film cloth by adjusting the refractive index ofthe organic-inorganic hybrid composition for the difference in therefractive indices between the organic-inorganic hybrid compositionafter curing and the glass cloth to be 0.01 or less.

DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram showing the process of manufacturing the compositefilm according to the present invention of which refractive index is notadjusted or the transparent composite film according to the presentinvention of which refractive index is adjusted;

FIG. 2 is a photograph showing the result of crack test of the compositefilms according to Comparative Example 1 and Example 1 of the presentinvention;

FIG. 3 is a photograph showing the comparison of light transmittance ofthe composite film according to Example 2 of which refractive index isnot adjusted to that of the glass cloth, and the transparent compositefilm according to Example 3 of which refractive index is adjusted tothat of the glass cloth; and

FIG. 4 is a photograph showing various glass cloths different in weavingdensity.

BEST MODE

The composite material according to the present invention comprises aglass cloth; and an organic-inorganic hybrid composition comprisingdiphenylsilanediol and alkoxy silane.

The glass cloth can be divided into various types depending on rawcomponents, thickness, and shape of the glass fiber, and divided intovarious types depending on weaving types of glass cloth and the numberof fiber per bundle, and may be selected therefrom.

The glass cloth may have a thickness of 10 to 200 μm.

The glass cloth has a refractive index of 1.51 (s-glass) to 1.56(e-glass).

The diphenylsilanediol is a main ingredient, and functions as a tanningmaterial to improve flexibility, which is a property required for thecomposite film.

The refractive index can be adjusted so that the organic-inorganichybrid composition, which uses the diphenylsilanediol and the metalalkoxide, has a refractive index, for instance, between 1.48˜1.60. Also,the crosslink structure of the metal alkoxide can be adjusted in orderto enhance the flexibility when the di-functional diphenylsilanediol andthe metal alkoxide are used together.

The alkoxy silane may be one or more selected frommethyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane,tetraethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, glycidyloxypropyltrimethoxysilane,aminopropyltriethoxysilane, and aminopropyltrimethoxysilane.

The organic-inorganic hybrid composition may contain 10 to 100 parts byweight of alkoxy silane, based on the 100 parts by weight ofdiphenylsilanediol.

The difference in the refractive indices between the organic-inorganichybrid composition after curing and the glass cloth may be 0.01 or less.The difference in the refractive index of 0.01 or less means that thedifference in the refractive index after curing organic-inorganic hybridcomposition and the refractive index of the glass cloth is 0.01 or less.Also, the refractive index after curing organic-inorganic hybridcomposition is defined as the index which is measured after curing onlythe organic-inorganic hybrid composition without including the glasscloth.

A transparent composite material and a transparent composite film (Referto example 1, 3, 4) can be provided when the difference in therefractive index is 0.01 or less between the organic-inorganic hybridcomposition and glass cloth after curing of the organic-inorganic hybridcomposition. A composite material and a composite film (Refer to example2) can be provided When the refractive index is not adjusted.

Any one of the diphenylsilanediol and alkoxy silane may have a higherrefractive index than that of the glass cloth; and the other one mayhave a lower refractive index than that of the glass cloth or the samerefractive index as that of the glass cloth.

In this connection, in the case of using a glass cloth having arefractive index of 1.51, the organic-inorganic hybrid composition mayinclude diphenylsilanediol having a refractive index of 1.513 that ishigher than that of the glass cloth, and alkoxy silane having arefractive index of 1.38˜1.51 that is lower or the same as that of theglass cloth. When the refractive index is measured after curing theorganic-inorganic hybrid composition, a difference in the refractiveindices between the organic-inorganic hybrid composition and the glasscloth may be 0.01 or less, preferably 0.005 or less. In this regard, atransparent composite material and a transparent composite film may beprovided.

The organic-inorganic hybrid composition according to the presentinvention may further include polymer and/or metal alkoxide. Here, thedifference in the birefringence can be reduced by wavelength when metalalkoxide is used.

The polymer may be preferably a thermoplastic resin, and more preferablya thermoplastic resin capable of transmitting visible light.

Examples of the thermoplastic resin may one or more selected frompolyolefins selected from the group consisting of low densitypolyethylene, high density polyethylene, ethylene-propylene copolymer,ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octenecopolymer, ethylene-norbornene copolymer, ethylene-DMON copolymer,polypropylene, ethylene-acetic acid vinyl copolymer,ethylene-methylmethacrylate copolymer, and ionomer resin; polyestersselected from the group consisting of polyethyleneterephthalate,polybutyleneterephthalate, and polyethylenenaphthalate; nylon-6, ornylon-6,6, metaxylenediamine-adipic acid condensation polymers;amide-based resins; acrylic resins; stylene-acrylonitrile resinsselected from the group consisting of polystylene orstylene-acrylonitrile copolymer, stylene-acrylonitrile-butadienecopolymer, and polyacrylonitrile; hydrophobic cellulose resins selectedfrom the group consisting of triacetic acid cellulose and diacetic acidcellulose; halogen containing resins selected from the group consistingof polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride,and polytetrafluoroethylene; hydrogen-bonding resins selected from thegroup consisting of polyvinylalcohol, ethylene-vinylalcohol copolymer,and cellulose derivative; polycarbonate; polysulfone; polyethersulfone;polyetheretherketone; polyphenyleneoxide; polymethyleneoxide; and liquidcrystal resins. In this connection, example of the acrylic resin mayinclude polymethylmethacrylate.

In addition, the resin used as the polymer preferably has good heatresistance, for example, a glass transition temperature (Tg) of 120 to300° C., more preferably 150 to 300° C., and most preferably 180 to 300°C.

Among the thermoplastic resins, examples of the resin having good heatresistance may include one or more selected from ethylene-norbornenecopolymer, ethylene-DMON copolymer, polyethyleneterephthalate,polyethylenenaphthalate, triacetic acid cellulose, diacetic acidcellulose, polyvinylidene chloride, polyvinylidene fluoride,polytetrafluoroethylene, polyvinylalcohol, ethylene-vinylalcoholcopolymer, polycarbonate, polysulfone, polyethersulfone,polyetheretherketone, and liquid crystal resin, and they may be usedalone or in combination of two or more thereof.

In the case where the organic-inorganic hybrid composition furtherincludes a polymer, the organic-inorganic hybrid composition may contain10 to 100 parts by weight of alkoxy silane and more than 0 and 100 orless parts by weight of the polymer, based on 100 parts by weight of thediphenylsilanediol.

In the case where the organic-inorganic hybrid composition comprises thediphenylsilanediol, alkoxy silane, and polymer, any one of them may havea higher refractive index than that of the glass cloth; another may havea lower refractive index than that of the glass cloth or the samerefractive index as that of the glass cloth; the other may have a lowerrefractive index than that of the glass cloth, the same refractive indexas that of the glass cloth, or a higher refractive index than that ofthe glass cloth. When the refractive index is measured after curing theorganic-inorganic hybrid composition, a difference in the refractiveindices between the organic-inorganic hybrid composition and the glasscloth may be 0.01 or less, and preferably 0.005 or less. In this regard,a transparent composite material and a transparent composite film may beprovided.

In this regard, in the case of using a glass cloth having a refractiveindex of 1.51, the organic-inorganic hybrid composition may includediphenylsilanediol having a refractive index of 1.513 that is higherthan that of the glass cloth, alkoxy silane having a refractive index of1.38 to 1.51 that is lower than or the same as that of the glass cloth,and a polymer having a refractive index of 1.51 to 1.78 that is the sameas or higher than that of the glass cloth. In this connection, as anexample of the polymer, polycarbonate having a refractive index of 1.586may be used, but is not limited thereto.

The metal alkoxide may be one or more selected from titanium butoxide,titanium propoxide, aluminum butoxide, and zirconium propoxide.

In the case where the organic-inorganic hybrid composition furtherincludes a polymer and metal alkoxide, the organic-inorganic hybridcomposition may contain 10 to 100 parts by weight of alkoxy silane, morethan 0 and 100 or less parts by weight of the polymer, and more than 0and 100 or less parts by weight of the metal alkoxide, based on 100parts by weight of diphenylsilanediol.

In the case where the organic-inorganic hybrid composition includesdiphenylsilanediol, alkoxy silane, polymer, and metal alkoxide, any oneof four components may have a higher refractive index than that of theglass cloth; another may have a lower refractive index than that of theglass cloth or the same refractive index as that of the glass cloth; theothers may each independently have a lower refractive index than that ofthe glass cloth, the same refractive index as that of the glass cloth,or a higher refractive index than that of the glass cloth.

When the refractive index is measured after curing the organic-inorganichybrid composition, a difference in the refractive indices between theorganic-inorganic hybrid composition and the glass cloth may be 0.01 orless, and preferably 0.005 or less. In this regard, a transparentcomposite material and a transparent composite film may be provided.

In this regard, in the case of using a glass cloth having a refractiveindex of 1.51, the organic-inorganic hybrid composition may includediphenylsilanediol having a refractive index of 1.513 that is higherthan that of the glass cloth, alkoxy silane having a refractive index of1.38 to 1.51 that is lower than or the same as that of the glass cloth,a polymer having a refractive index of 1.51 to 1.78 that is the same asor higher than that of the glass cloth, and metal alkoxide having arefractive index of 1.7 to 2.7 that is higher than that of the glasscloth. In this connection, as an example of the polymer, polycarbonatehaving a refractive index of 1.586 may be used, but is not limitedthereto.

The composite film according to the present invention is manufactured byusing the composite material according to the present invention toinclude the glass cloth; and the organic-inorganic hybrid compositioncontaining diphenylsilanediol and alkoxy silane. Specific descriptionwill be omitted since the above-mentioned description will be equallyapplied hereto.

The organic-inorganic hybrid composition may further include polymerand/or metal alkoxide.

In this regard, a difference in the refractive indices between theorganic-inorganic hybrid composition after curing and the glass cloth is0.01 or less provided is a transparent composite film.

A transparent composite film (Refer to example 1, 3, 4) can be providedwhen the difference in the refractive index is 0.01 or less between theorganic-inorganic hybrid composition and glass cloth after curing of theorganic-inorganic hybrid composition. When the refractive index is notadjusted a transparent composite film can be provided. (Refer to example2)

A transparent composite film (Refer to example 1, 3, 4) can be providedwhen the difference in the refractive index is 0.01 or less between theorganic-inorganic hybrid composition and glass cloth after curing of theorganic-inorganic hybrid composition. A composite film (Refer to example2) can be provided When the refractive index is not adjusted.

The composite film or transparent composite film according to thepresent invention may be used as a substrate and a functional film ofvarious electronic devices such as a substrate of various displaydevices, a substrate of solar cell, and a functional film of displaydevice.

For example, the composite film or the transparent composite filmaccording to the present invention may be used as a substrate of liquidcrystal display (LCD), a substrate of color filter, a substrate oforganic EL display device, and an optical film of display device, but isnot limited thereto.

On the other hand, the electronic device according to the presentinvention may include the composite film or the transparent compositefilm according to the present invention.

Examples of the electronic device may include various display devicesand solar cells.

The method of manufacturing the composite film according to the presentinvention may comprises the steps of a) preparing a glass cloth; b)preparing an organic-inorganic hybrid composition in a sol state,comprising diphenylsilanediol and alkoxy silane; and c) dipping andcuring the glass cloth in the organic-inorganic hybrid composition in asol state (see FIG. 1).

Accordingly, the adhesion strength between the composition and the glassfiber is improved by the sol-gel reaction between the organic-inorganichybrid composition and the glass cloth, and the improved adhesionstrength provides the prepared transparent composite film withcrack-free property.

The glass cloth may be divided into various types depending on rawcomponents, thickness, and shape of the glass fiber, and divided intovarious types depending on weaving types of glass cloth and the numberof fiber per bundle, and may be selected therefrom.

The glass cloth may have a thickness of 10 to 200 μm.

The glass cloth has a refractive index of 1.51 (s-glass) to 1.56(e-glass).

The diphenylsilanediol is a main ingredient, and functions as a tanningmaterial to improve flexibility, which is a property required for thecomposite film.

Specifically, diphenylsilanediol is used with alkoxy silane to controlthe degree of the cross-linking density, thereby improving theflexibility of the composite film.

When the diphenylsilanediol of low partial hydrolysis is used withalkoxy silane, the glass cloth is easily dipped in the organic-inorganichybrid composition containing the diphenylsilanediol, thereby preventinggeneration of air bubble on the composite film and manufacturing thecrack-free composite film.

As such, in the case of adding diphenylsilanediol, the flexibility ofthe composite film is ensured, thereby providing a composite film havinggood heat resistance and dimensional stability.

The alkoxy silane may be one or more selected frommethyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane,tetraethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, glycidyloxypropyltrimethoxysilane,aminopropyltriethoxysilane, and aminopropyltrimethoxysilane.

The organic-inorganic hybrid composition may contain 10 to 100 parts byweight of alkoxy silane, based on 100 parts by weight ofdiphenylsilanediol.

A difference in the refractive indices between the organic-inorganichybrid composition after curing and the glass cloth may be 0.01 or less,and thus a transparent composite film may be provided. When adjustingthe refractive index of the organic-inorganic hybrid composition for thedifference in the refractive indices between the organic-inorganichybrid composition after curing and the glass cloth to be 0.01 or less,the method of manufacturing the transparent composite film can beprovided (Refer to FIG. 1).

Like this, When adjusting the refractive index of the organic-inorganichybrid composition for the difference in the refractive indices betweenthe organic-inorganic hybrid composition after curing and the glasscloth to be 0.01 or less, the method of manufacturing the transparentcomposite film can be provided. And if the refractive index is notcontrolled, the composite film manufacturing method can be provided.

Any one of the diphenylsilanediol and alkoxy silane may have a higherrefractive index than that of the glass cloth; and the other one mayhave a lower refractive index than that of the glass cloth or the samerefractive index as that of the glass cloth.

In this connection, in the case of using a glass cloth having arefractive index of 1.51, the organic-inorganic hybrid composition mayinclude diphenylsilanediol having a refractive index of 1.513 that ishigher than that of the glass cloth, and alkoxy silane having arefractive index of 1.38˜1.51 that is lower or the same as that of theglass cloth. When the refractive index is measured after curing theorganic-inorganic hybrid composition, a difference in the refractiveindices between the organic-inorganic hybrid composition and the glasscloth may be 0.01 or less, preferably 0.005 or less. In this regard, atransparent composite film may be provided.

The organic-inorganic hybrid composition according to the presentinvention may further include polymer and/or metal alkoxide.

The polymer may be preferably a thermoplastic resin, and more preferablya transparent thermoplastic resin capable of transmitting visible light.

Examples of the thermoplastic resin may include one or more selectedfrom polyolefins selected from the group consisting of low densitypolyethylene, high density polyethylene, ethylene-propylene copolymer,ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octenecopolymer, ethylene-norbornene copolymer, ethylene-DMON copolymer,polypropylene, ethylene-acetic acid vinyl copolymer,ethylene-methylmethacrylate copolymer, and ionomer resin; polyesterselected from the group consisting of polyethyleneterephthalate,polybutyleneterephthalate, and polyethylenenaphthalate; nylon-6, ornylon-6,6, metaxylenediamine-adipic acid condensation polymer;amide-based resin; acrylic resin; stylene-acrylonitrile resins selectedfrom the group consisting of polystylene or stylene-acrylonitrilecopolymer, stylene-acrylonitrile-butadiene copolymer, andpolyacrylonitrile; hydrophobic cellulose resins selected from the groupconsisting of triacetic acid cellulose and diacetic acid cellulose;halogen containing resins selected from the group consisting ofpolyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride,and polytetrafluoroethylene; hydrogen-bonding resins selected from thegroup consisting of polyvinylalcohol, ethylene-vinylalcohol copolymer,and cellulose derivative; polycarbonate; polysulfone; polyethersulfone;polyetheretherketone; polyphenyleneoxide; polymethyleneoxide; and liquidcrystal resins. In this connection, example of the amide-based resin mayinclude polymethylmethacrylimide, and example of the acrylic resin mayinclude polymethylmethacrylate.

The resin used as the polymer preferably has good heat resistance, forexample, a glass transition temperature (Tg) of 120 to 300° C., morepreferably 150 to 300° C., and most preferably 180 to 300° C.

Among the thermoplastic resins, examples of the resin having good heatresistance may include one or more selected from ethylene-norbornenecopolymer, ethylene-DMON copolymer, polyethyleneterephthalate,polyethylenenaphthalate, triacetic acid cellulose, diacetic acidcellulose, polyvinylidene chloride, polyvinylidene fluoride,polytetrafluoroethylene, polyvinylalcohol, ethylene-vinylalcoholcopolymer, polycarbonate, polysulfone, polyethersulfone,polyetheretherketone, and liquid crystal resin, and they may be usedalone or in combination of two or more thereof.

In the case where the organic-inorganic hybrid composition furtherincludes the polymer, the organic-inorganic hybrid composition maycontain 10 to 100 parts by weight of alkoxy silane and more than 0 and100 or less parts by weight of the polymer, based on 100 parts by weightof the diphenylsilanediol.

In the case where the organic-inorganic hybrid composition includesdiphenylsilanediol, alkoxy silane, and polymer, any one of them may havea higher refractive index than that of the glass cloth; another may havea lower refractive index than that of the glass cloth or the samerefractive index as that of the glass cloth; the other may have a lowerrefractive index than that of the glass cloth, the same refractive indexas that of the glass cloth, or a higher refractive index than that ofthe glass cloth. When the refractive index is measured after curing theorganic-inorganic hybrid composition, a difference in the refractiveindices between the organic-inorganic hybrid composition and the glasscloth may be 0.01 or less, and preferably 0.005 or less. In this regard,a transparent composite film may be provided.

In this regard, in the case of using a glass cloth having a refractiveindex of 1.51, the organic-inorganic hybrid composition may includediphenylsilanediol having a refractive index of 1.513 that is higherthan that of the glass cloth, alkoxy silane having a refractive index of1.38 to 1.51 that is lower than or the same as that of the glass cloth,and a polymer having a refractive index of 1.51 to 1.78 that is the sameas or higher than that of the glass cloth. In this connection, as anexample of the polymer, polycarbonate having a refractive index of 1.586may be used, but is not limited thereto.

The metal alkoxide may be one or more selected from titanium butoxide,titanium propoxide, aluminum butoxide, and zirconium propoxide.

In the case where the organic-inorganic hybrid composition furtherincludes the polymer and metal alkoxide, the organic-inorganic hybridcomposition may contain 10 to 100 parts by weight of alkoxy silane; morethan 0 and 100 or less parts by weight of the polymer; and more than 0and 100 or less parts by weight of the metal alkoxide, based on 100parts by weight of diphenylsilanediol.

Specifically, 10 to 100 parts by weight of alkoxy silane and more than 0and 100 or less parts by weight of the metal alkoxide were mixed, basedon 100 parts by weight of diphenylsilanediol, 100 parts by weight ofdiphenylsilanediol, and then more than 0 and 100 or less parts by weightof distilled water is added, based on 100 parts by weight ofdiphenylsilanediol, followed by partial hydrolysis at a temperaturerange of 25 to 100° C. for 10 min to 24 hrs. Then, more than 0 and 100or less parts by weight of the polymer is added thereto, based on 100parts by weight of diphenylsilanediol to manufacture theorganic-inorganic hybrid composition.

In step b), to manufacture a stable organic-inorganic hybrid compositionhaving a low viscosity in a sol state, the reaction may be subjected at0° C. to 100° C., preferably 0° C. to 50° C., and most preferably 0° C.to 25° C.

In step b), upon manufacturing the organic-inorganic hybrid compositionin a sol state, the reaction is slowly subjected at 25° C. to preventrapid gelation of the organic-inorganic hybrid composition.

In the case where the organic-inorganic hybrid composition includesdiphenylsilanediol, alkoxy silane, polymer, and metal alkoxide, any oneof four components may have a higher refractive index than that of theglass cloth; another may have a lower refractive index than that of theglass cloth or the same refractive index as that of the glass cloth; theothers may each independently have a lower refractive index than that ofthe glass cloth, the same refractive index as that of the glass cloth,or a higher refractive index than that of the glass cloth.

When the refractive index is measured after curing the organic-inorganichybrid composition, a difference in the refractive indices between theorganic-inorganic hybrid composition and the glass cloth may be 0.01 orless, and preferably 0.005 or less. In this regard, a transparentcomposite film may be provided.

In this regard, in the case of using a glass cloth having a refractiveindex of 1.51, the organic-inorganic hybrid composition may includediphenylsilanediol having a refractive index of 1.513 that is higherthan that of the glass cloth, alkoxy silane having a refractive index of1.38 to 1.51 that is lower than or the same as that of the glass cloth,a polymer having a refractive index of 1.51 to 1.78 that is the same asor higher than that of the glass cloth, and metal alkoxide having arefractive index of 1.7 to 2.7 that is higher than that of the glasscloth. In this connection, as an example of the polymer, polycarbonatehaving a refractive index of 1.586 may be used, but is not limitedthereto.

Step c) may be repeated at least once. That is, after the glass cloth isdipped in the organic-inorganic hybrid composition in a sol state, thecuring process may be performed once, or repeated several times. Thecontinuous process of dipping and curing the glass cloth in theorganic-inorganic hybrid composition having a low viscosity and a shortcuring time is repeated several times to manufacture the transparentcomposite film, thereby improving the productivity.

In step c), the glass cloth burned in an oxygen furnace at 500 to 700°C. for 10 to 60 min may be used. When the burned glass cloth is used,the organic material adsorbed on the surface of the glass cloth can beremoved, thereby improving adhesion between the dipping solution and thesurface of glass cloth.

In step c), after the glass cloth is dipped in the organic-inorganichybrid composition in a sol state, the glass cloth can be cured at 50 to300° C. for 5 min to 2 hrs. The organic-inorganic hybrid has a shortcuring time to improve productivity of the transparent composite film,whereas a longer processing time for curing or solvent evaporation isrequired in the case of using the known epoxy and polymers.

The present invention provides a composite film or a transparentcomposite film manufactured by the above described method.

MODE FOR INVENTION

Hereinafter, the present invention will be described in more detail withreference to the accompanying Drawings and Examples. However, theseExamples are for illustrative purposes only, and the invention is notintended to be limited by these Examples.

Example 1

100.0 parts by weight of diphenylsilanediol (refractive index beforecuring: 1.513), 32.5 parts by weight of tetraethoxysilane (refractiveindex before curing: 1.382), 64.0 parts by weight ofglycidyloxypropyltrimethoxysilane (refractive index before curing:1.429), 0.5 part by weight of aminopropyltrimethoxysilane (refractiveindex before curing: 1.424), 2.0 parts by weight of aluminum butoxide(refractive index before curing: 1.439, refractive index after curing:1.7), and 1.0 part by weight of zirconium propoxide (refractive indexbefore curing: 1.451, refractive index after curing: 2.2) were mixedtogether, and 80.0 parts by weight of distilled water was added thereto,followed by hydrolysis at 25° C. for 24 hrs to prepare anorganic-inorganic hybrid composition in a sol state. 5 parts by weightof polyarylate was added thereto to prepare a dipping organic-inorganichybrid composition in a sol state.

To remove organic materials on the surface, the glass cloth (thickness:50 μm, refractive index: 1.51) prepared by using S-glass that was burnedin an oxygen furnace at 500° C. for 10 min was primarily dipped in thedipping organic-inorganic hybrid composition in a sol state, and thenresidual solvent was removed at room temperature for 1 min, followed byprimary curing at a 120° C. oven for 5 min.

After curing, second dipping and curing were performed in the samemanners as the primary dipping and curing to manufacture a transparentcomposite film.

Example 2

A composite film was manufactured in the same manners as in Example 1,except for adding no aluminum butoxide, zirconium propoxide, andpolyarylate upon the preparation of the dipping organic-inorganic hybridcomposition in a sol state.

Example 3

100.0 parts by weight of diphenylsilanediol (refractive index beforecuring: 1.513), 32.5 parts by weight of tetraethoxysilane (refractiveindex before curing: 1.382), 64.0 parts by weight ofglycidyloxypropyltrimethoxysilane (refractive index before curing:1.429), 0.5 part by weight of aminopropyltrimethoxysilane (refractiveindex before curing: 1.424), 2.0 parts by weight of aluminum butoxide(refractive index before curing: 1.439, refractive index after curing:1.7), 1.0 part by weight of zirconium propoxide (refractive index beforecuring: 1.451, refractive index after curing: 2.2), and 30.0 parts byweight of titaniumbutoxide (refractive index before curing: 1.49,refractive index after curing: 2.7) were mixed together, and 80.0 partsby weight of distilled water was added thereto, followed by hydrolysisat 25° C. for 24 hrs to prepare an organic-inorganic hybrid compositionin a sol state. 5 parts by weight of polyarylate was added thereto toprepare a dipping organic-inorganic hybrid composition in a sol state.

To remove organic materials on the surface, the glass cloth (thickness:50 μm, refractive index: 1.56) prepared by using E-glass that was burnedin an oxygen furnace at 500° C. for 10 min was primarily dipped in thedipping organic-inorganic hybrid composition in a sol state, and thenresidual solvent was removed at room temperature for 1 min, followed byprimary curing at a 120° C. oven for 5 min.

After curing, second dipping and curing were performed in the samemanners as the primary dipping and curing to manufacture a transparentcomposite film.

Example 4

A transparent composite film was manufactured in the same manners as inExample 3, except for adding no aluminum butoxide, zirconium propoxide,and polyarylate upon the preparation of the dipping organic-inorganichybrid composition in a sol state and using S-glass instead of E-glass.

Comparative Example 1

100 parts by weight of epoxy compound (trade name: ERL-4221, DowChemical), 134 parts by weight of a curing agent, ANHYDRIDE (MH700G, NewJapan Chemical), 2 parts by weight of triphenylphosphonium bromide, and150 parts by weight of methylethylketone were mixed together, and thenthe glass cloth (thickness: 50 μm, refractive index: 1.56) prepared byusing S-glass that was dipped in the prepared dipping solution, followedby sequential curing at 100° C. for 2 hrs, at 120° C. for 2 hrs, at 150°C. for 2 hrs, at 200° C. for 2 hrs, and at 240° C. for 2 hrs tomanufacture a composite film.

Comparative Example 2

A composite film was manufactured in the same manners as in Example 1,except for using no diphenylsilanediol.

Experimental Example

The thickness of the composite films according to Examples 1 to 4 andthe composite film according to Comparative Example 1 to 2 were measuredusing a scanning electron microscope (SEM), and a coefficient of thermalexpansion and a glass transition temperature thereof were measured, anda crack test was performed. The results are shown in Table 1, and FIGS.2 and 3. Also Refractive index and Light transmittance were measured.

The refractive index of the glass cloth in table 1 is acquired bymeasuring the glass cloth prior to respectively dipping the glass clothin the dipping organic-inorganic hybrid composition of examples 1˜4 andcomparative example 2; and also dipping the glass cloth in the dippingsolution of comparative example 1. Thus, this index is the innaterefractive index of the glass cloth.

The refractive index that is measured after the curing which is shown intable 1 has been obtained by measuring the dipping organic-inorganichybrid composition of examples 1˜4 and comparative example 2 withoutdipping of the glass cloth and the dipping solution of comparativeexample 1 without dipping of the glass cloth; curing only the dippingorganic-inorganic hybrid composition manufactured in comparativeexamples 1˜4 and comparative example 2, and also curing the dippingsolution manufactured in comparative example 1; and respectivelymeasuring the cured materials thereof. The refractive index of thecomposition after curing in table 1 is that of only the composition ofthe example 1˜4 and comparative example 2, and the dipping solution ofthe comparative example 1, wherein curing occurs without including theglass cloth.

And the light transmittance under table 1 has been measured by measuringthe light transmittance rate of the film that was manufactured bydipping the glass cloth in the organic-inorganic hybrid composition ofthe examples 1˜4 and comparative example 2, and the dipping solution ofcomparative example 1; and then curing, respectively.

Measurement conditions were as follows.

1) Coefficient of thermal expansion: Measurement was made in accordancewith ASTM D696 at a rate of temperature rise of 10° C. per min and astress of 5 gf using a thermomechnical analyzer (TMA), and pencilhardness was measured at a load of 200 g in accordance with ASTM D3363.

2) Glass transition temperature (Tg): Measurement was made using adifferential scanning calorimeter (DSC; TA Instrument, DSC2010) at arate of temperature rise of 10° C. per min.

3) Refractive index: Measurement was made using a refractometer (ATAGO,DR-M4) at 589 nm.

4) Light transmittance: Measurement was made in accordance with ASTMD1003 using a UV-spectrometer (Varian) at a visible range of 380 to 780nm.

5) Crack test: a cylinder having a diameter of 1 cm is wrapped with thefilm, and then crack generation was observed.

TABLE 1 Coefficient of Refractive Thickness thermal Refractive index ofLight (SEM result) expansion(ppm/ Crack index of glass compositiontransmittance (μm) K) Tg (° C.) test cloth after curing (%) Example 1 5517 230 No crack 1.510 1.5103 85 Example 2 59 18 221 No crack 1.5101.4806 23 Example 3 55 17 230 No crack 1.560 1.5604 82 Example 4 60 18220 No crack 1.510 1.5106 81 Comparative 60 19 210 crack 1.510 1.5101 79Example 1 Comparative 58 18 210 crack 1.510 1.5216 65 Example 2

The composite films of Examples 1 to 4 according to the presentinvention were found to have a thickness of 55, 59, 55 and 60 μm, acoefficient of thermal expansion of 17, 18, 17 and 18 ppm/K, and a glasstransition temperature of 230, 221, 230 and 220° C., respectively. Thus,in the case of using the composite films according to Examples 1 to 4 ofthe present invention as a substrate of display device, it can be seenthat the thickness, coefficient of thermal expansion, and glasstransition temperature are suitable for the substrate of display device.

In addition, a bending test was performed to observe the crackgeneration. As shown in FIG. 2 and table 1, cracks were found to begenerated in the composite film according to Comparative Examples 1 to2. In contrast, the composite film according to Examples 1 to 4 werefound to have no crack at the interface between glass fibers, owing toexcellent interface adhesion strength between the glass cloth andorganic-inorganic hybrid composition.

In addition, as shown in FIG. 2, air bubbles were found to be generatedin the composite film according to Comparative Example 1. In contrast,the composite film according to Example 1 was found to have no airbubble, owing to excellent interface adhesion strength between the glasscloth and organic-inorganic hybrid composition.

Also, the refractive index was not adjusted in example 2 in order toprovide the composite film that does not request high transparency,however, in the case of examples 1,3, and 4, it is verified in table 1and FIG. 3 that transparent composite film can be provided due to highlight transmittance rate (%) by adjusting the refractive index of theorganic-inorganic hybrid composition based on the refractive index ofthe glass cloth in order to provide transparent composite film requiringhigh transparency.

In particular, in the case of examples 1, 3 and 4, the refractive indexof the organic-inorganic hybrid composition is adjusted in order thatthe difference between the refractive index of the organic-inorganichybrid composition after curing and that of the glass cloth is 0.01 orless on the basis of the refractive index of the used glass cloth. Andin the case of example 2, the difference between the refractive index ismore than 0.01.

From the photos under table 1 and FIG. 3, one can see that in example 2where the refractive index is not adjusted, the light transmittance rateis 23% thereby being able to be used as composite film that does notrequire high transparency rate. Also, in example 1 and 4, where therefractive index is set at 1.51 to be of S-glass and also in example 3where the refractive index is set at 1.56 to be E-glass, thetransparency rate was 85%, 81%, and 82% respectively. Accordingly, onecan see that they can be used the transparent composite film providinghigh transparency rate due to high transparency.

Thus, according to the present invention, the composite film ismanufactured by using a tightly woven glass cloth and anorganic-inorganic hybrid composition having low viscosity and highreactivity, thereby providing an air bubble- and crack-free compositefilm.

In addition, the composite film according to the present inventionmaintains properties including low coefficient of thermal expansion(CTE), low heat deformation, high heat resistance and high flexibilitythat are basic properties of glass cloth, while having a cross-linkedorganic-inorganic hybrid structure, and thus the composite filmaccording to the present invention can be used at a high temperatureregardless of glass transition temperature (Tg).

Further, according to the present invention, in the case of adjustingthe refractive index of the organic-inorganic hybrid composition for thedifference in the refractive indices between the organic-inorganichybrid composition after curing and the glass cloth to be 0.01 or less,thereby easily manufacturing a transparent composite film capable ofbeing used as a transparent substrate.

1-15. (canceled)
 16. A method for manufacturing a composite film,comprising the steps of: a) preparing a glass cloth; b) preparing anorganic-inorganic hybrid composition in a sol state, comprisingdiphenylsilanediol and alkoxy silane; and c) dipping and curing theglass cloth in the organic-inorganic hybrid composition in a sol state.17. The method for manufacturing a composite film according to claim 16,wherein in step a), the glass cloth has a thickness of 10 to 200 μm. 18.The method for manufacturing a composite film according to claim 16,wherein a difference in the refractive indices between theorganic-inorganic hybrid composition after curing and the glass cloth is0.01 or less. 19-26. (canceled)
 27. The method for manufacturing acomposite film according to claim 16, wherein the step c) is repeatedonce or more.
 28. The method for manufacturing a composite filmaccording to claim 16, wherein in step c), the glass cloth burned in anoxygen furnace at 500 to 700° C. for 10 to 60 min is used.
 29. Themethod for manufacturing a composite film according to claim 16, whereinin step c), the glass cloth is dipped in the organic-inorganic hybridcomposition in a sol state, and then cured at 50 to 300° C. for 5 min to2 hrs.